Leak Detection Safeguarding

Stamicarbon’s High Pressure Urea

Vessels
Urea solutions are not very corrosive, but ammonium carbamate, an intermediate in urea synthesis is
highly corrosive. To protect the carbon steel high pressure synthesis equipment from corrosion,
stainless steel loose liners are commonly applied. With a loose liner a hazardous situation may arise if
a leak occurs and carbamate containing fluids enters the space between liner and carbon steel. For this
reason Stamicarbon designed a system which continuously monitors for leaks to allow safe operation
of said equipment.

Alex Scheerder
Stamicarbon BV, the Netherlands

Introduction

U
rea is synthesized from ammonia and
carbon dioxide at pressures of about
145 bar (2200 psi) and temperatures of
183 °C (360 °F). In a modern Stamicarbon world
scale (~ 3500 mtpd) urea plant the synthesis
section consists of three high pressure vessels;
Pool Condenser, Urea Reactor and HP Stripper,
see Figure 1.
Figure 1: Modern Stamicarbon (Avancore®) Urea
Ammonia, carbon dioxide and urea are not very Plant highlighting HP Urea Synthesis equipment
corrosive, but the synthesis solution becomes
highly corrosive due to ammonium carbamate Undetected carbamate corrosion of the carbon
formed as intermediate step in the synthesis of steel pressure shell of urea vessels can lead to
urea. For instance, ammonium carbamate catastrophic failures. To avoid corrosion of the
solutions in contact with carbon steel will cause carbon steel shell Stamicarbon applies special
corrosion rates in excess of 900 mm per year. steel grades such as Safurex®, strict

2010 77 AMMONIA TECHNICAL MANUAL

 specifications as to the quality and welding of
these steels and strict design requirements with
respect to the application of the protective
corrosion resistant layer.
This corrosion resistant layer can be applied as a
loose liner, a weld overlay or as an explosive
cladding.
A weld overlay is commonly used on carbon
steel tube sheets of heat exchangers (Pool
Condenser, HP Stripper) or on small surface
areas such as for instance hemi-heads, nozzles,
etc.
Passage ways underneath loose liner
Loose liner plates are welded onto the carbon
steel pressure shell, forming liner compartments.
The confined space of each compartment is
monitored for leakages. The liner weld is the
most critical part with respect to the risk for
leakages. To enhance the probability to detect a
leak each liner compartment is equipped with
passageways including two leak detection holes
through the pressure shell. The passageways are
machined in the pressure vessel wall parallel to
the buffer layer to fix the liner plates, see Figure
2 and Photo1.

For larger surface areas (shell of Pool Condenser

or Urea Reactor) it is economically more feasible
to apply a loose liner.

Having a loose liner, a hazardous situation may

arise if a leak occurs and carbamate containing
fluids enter the space between the liner and
carbon steel pressure shell. This leads to
corrosion of the carbon steel and will weaken the
pressure vessel wall. Vessels having a liner Figure 2: Principle of leak detection in HP urea
installed are equipped with an early warning vessel with loose liner
system for carbamate leakages.

Stamicarbon designed a leak detection system

with continuous monitoring to allow safe
operation of the said vessels.

System outline

The leak detection system consists of three parts:

• Passage ways underneath loose liner
• Piping system and headers Photo 1: Leak detection passageways machined in
• Monitor system c-steel hemi-head

AMMONIA TECHNICAL MANUAL 78 2010

 Piping system and headers
The confined space of each liner compartment is
connected to the leak monitor with pipes and
headers, see Photo 2. The piping must be gas
tight, in order to avoid false indications. To
avoid crystallization of the urea / ammonia
carbamate solution the temperature of the piping
system must be kept above 135 °C (275 °F). This
can be done by heating or insulating the piping.
Photo 2: Header of Pool Condenser
The headers of all vessels are connected in
parallel to the main header, which in turn is
connected to the leak monitor. In each pipe line
towards the header a block valve is installed to
make it possible to isolate circuits and to localize
any leaks detected. Also block valves are
mounted on the main header in order to
determine which vessel is leaking.
Monitor
An electrochemical sensor that allows
continuous ammonia gas detection is used for
leak detection, see Photo 3.
Ammonia is chosen as leak agent since it is
present throughout the whole synthesis section of
the plant and is easy to detect. Also carbamate
leaking behind the liner will dissociate into
ammonia and carbon dioxide since the pressure
behind the liner is atmospheric. An important
2010
feature for reliable leak detection is the property
of ammonia to emerge readily through moisture.
Photo 3: Ammonia gas detector
Features
The features of the Stamicarbon leak detection
system are:
1. Accurate detection.
2. Detection of a gas leak of 1 x 10-7 STD.cc
/sec1 is possible.
3. The response time (i.e. the time elapsing
before a leak is detected) is less than 60
minutes.
4. The location of the leak can be traced.
5. The leakage rate can be calculated.
6. More than one piece of equipment can be
connected to the gas monitor.
It should be taken into account that the synthesis
composition varies throughout the HP loop.
Therefore the composition of fluid leaking
behind the liner will also differ from one place to
another and thus the ammonia concentrations
will differ. This will influence the ammonia
1
Leakage rates are normally indicated in STD.cc/sec.
(standard cubic centimeters per second)
79 AMMONIA TECHNICAL MANUAL
 concentrations measured and must be taken into
account for calculating the leak rate.
A quick response time is needed because the
synthesis solution leaking away between liner
and carbon steel pressure shell not only contains
the corrosive ammonium carbamate but also
urea. This synthesis solution will partly
dissociate and finally crystallize as biuret or
triuret, with the risk that detection becomes
impossible due to blockage of the passage ways.
Flow type leak detection system
The flow type leak detection system can be used
in all new equipment since they are equipped
with the grooved passageways system and at
least two leak detection holes in each liner
compartment. In the gap between liner and
pressure shell instrument air is circulated, see
Figure 3. The air must be dried before entering
the gas monitor.

Operating principles

The annular space between the carbon steel

pressure shell and liner, together with the leak
detection holes, is connected to the gas monitor
via headers/coolers. The air present in this
Figure 3: Flow type leak-detection system
system is brought to the monitor with help of
plant instrument air. The monitor provides a
During circulation, the resistance is not the same
continuous indication of gaseous ammonia
in each liner compartment. To equalize this, a
concentrations. The monitor operates with help
flow meter and a control valve are required in the
of an electrochemical sensor, allowing analyzing
piping to the header to optimize the flow in each
ammonia concentrations up to 1,000 ppm in a
liner compartment. The piping of each liner
mixture of gases.
compartment ends in a header/cooler in which
the air is cooled down to ambient.
Stamicarbon has two concepts for leak detection
available.
A small part of the air is fed into the gas monitor
- A flow type leak detection system.
to analyze ammonia continuously. The
- A vacuum type leak detection system.
remaining air is released to atmosphere.
Whether a flow or a vacuum type leak detection
A reducing valve permits supply of instrument
system should be utilized, depends on the
air into the system. If the pressure drops as a
possibility to circulate gas through the liner
result of a leak developing in the connecting
compartments. The vacuum type leak detection
tubing or as a result of a shut-down, air will be
system is suitable for older equipment having no
supplied too. A flow meter is used to signal such
passage way grooves and only one leak detection
a pressure drop.
hole. Circulation of air is not possible in this
case.

AMMONIA TECHNICAL MANUAL 80 2010

 A safety valve prevents that the pressure in the
system becomes too high.
Vacuum type leak detection system
In case no passageway system is present between
lining and pressure shell, it is advisable to use
the vacuum system, see Figure 4.
Figure 4: Vacuum Type Leak Detection System
Fluids leaking from a liner are continuously
sucked to a monitor by means of a vacuum
pump.
The piping of each liner compartments ends in a
header/cooler, in which the air is collected, dried
and cooled down.
Then the air is sucked into a gas monitor in
which the ammonia concentration is
continuously measured. Air leaving is discharged
through the flow indicator and a seal vessel. The
seal vessel prevents air contaminated with
ammonia from entering the leak detection
system.
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Operations & Maintenance
It is of importance to commission and operate
the leak detection system according to the
guidelines. During commissioning and plant shut
down, care must be taken not to over pressurize
the leak detection system. The system is
safeguarded at 0.5 barg. Higher pressures may
lead to bulging or even rupture of liner segments.
Small leak indications must be monitored closely
and in case the leak becomes big enough to
locate, the plant must be stopped to find and
repair the leak. In this way corrosion damages to
the carbon steel pressure shell can be avoided.
A leak indication which suddenly stops is of
potential risk for corrosion damage of the carbon
steel shell. The plant must be stopped
immediately to locate and repair this leak.
Proper function of the system must be checked
on regular basis. Blockage of the leak detection
system (for instance due to crystallized product
leaking behind the liner) will hamper leak
detection and may lead to a dangerous situation.
Stamicarbon does not recommend using steam
condensate to open up blocked leak detection
systems, see chapter 6.
Locating leaks
The liner compartment, in which a leak occurs,
can be traced by searching each compartment
with help of the valves on the header. When the
leaking compartment and the ammonia content
are known, the leak rate can be calculated. This
rate gives an indication about the probability to
find the leak and which method to use.
81 AMMONIA TECHNICAL MANUAL
 There are two methods recommended for finding
a leak:
● Bubble test
● Ammonia leakage test
Bubble test
In case the leak is big enough, a bubble test is an
appropriate method. The pressure in the gap
between the liner and carbon steel shell is
increased to maximum 0.3 barg using air or
nitrogen.
Detectable leak rate using the bubble method is
in the range of 1*10-3 STD.cc/s.
Ammonia leak test
For smaller leaks an ammonia leak test is
advised. Ammonia is introduced behind the liner
with a maximum pressure of 0.03 barg. Before
applying the ammonia the air is evacuated
behind the liner by a vacuum pump.
The detection ability of small leaks depends on
the time for the ammonia to penetrate the leak, as
indicated in Figure 5.
After a dwell time of 8 to 10 hours leaks with a
leak rate as small as 0.02 to 0.03 cc/hr becomes
detectable. Ammonia sensitive spray or paste is
applied onto the welds to be inspected.
Leaks are detected by a color change of the paste
or sprayed solution. Detectable leak rate is about
1000 times better compared to the air bubble
test; ~ 1*10-6 STD.cc/s.
For finding smaller leaks (leak detection system
is able to detect leaks as small as 1*10-7
STD.cc/s), other strategies must be tried, see
chapter 6.
AMMONIA TECHNICAL MANUAL
Figure 5: Detection sensitivity of NH3 leak test
Helium or Freon gases are not recommended for
findings leaks.
Helium is not able to pass through moisture,
which will be present behind the liner after a
leak. In case the leak path is completely filled
with moisture, Helium will not indicate the leak.
Furthermore with this method it is difficult to
pinpoint (locate) the leak.
Freon is not recommended since any Freon left
behind the liner could lead to chloride stress
corrosion cracking.
Case histories
Finding a very small leak
In a urea plant the leak detection system
indicated a very small leak in the Urea Reactor.
Despite the fact that the leak was too small to
localize plant management decided to stop the
plant.
However the leak could not be located by neither
bubble nor ammonia leak test.
In order to find the leak the following strategy
was followed. It was decided to pressurize the
vessel with carbon dioxide and to dip the leak
82 2010
 detection tubes into a water bottle
schematically presented in Figure 6.
At a certain pressure the leak became visible by
bubbling of carbon dioxide gas in the water
bottle. Keeping the pressure at this level the urea
reactor was subsequently filled with water until
the bubbling stopped. Water filling was stopped
and the water level indicated the area where to
search for the leak (just below the water level).
Figure 6: Pressure test method to locate leak in
Urea Reactor
Eventually the leak was located and repaired.
Ultrasonic wall thickness measurements of the
carbon steel pressure shell proved that no
corrosion occurred and the reactor could be
operated safely without any constrains.
Opening of blocked liner segments
One of the urea plants suffered from blockages
of the leak detection system in the Urea Reactor.
To open the leak detection system steam
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as condensate was used which was readily available
in the plant. In this way it was possible to open
up the leak detection system.
For this particular Urea Reactor a partial relining
of the top channel was scheduled during a
planned turnaround. Relining was due since the
liner (316L urea grade) became too thin due to
the corrosion at process side. The lifetime of a
316L UG liner of nominal thickness of 8 mm is
typically 20 years. Stamicarbon advises to
remove the old liner before installing a new liner.
This has two reasons:
• To have again a proper function leak
detection system in place after re-lining.
• To have the opportunity to check the carbon
steel pressure shell.
After removing the old liner, severe corrosion
was observed in the carbon steel pressure shell,
see Photo 4. General corrosion resulting in wall
thinning as well as Trans-granular Stress
Corrosion Cracks (TRSCC) was observed.
Except for this Urea Reactor no TRSCC in other
Urea Reactors was established in the casuistry of
Stamicarbon urea plants. The root cause of this
corrosion most likely was the presence of
potassium in the gap behind the liner, whereby
the forming of KHCO3 / KCO3 KH causes the
Stress Corrosion Cracking (SCC). It is believed
that the potassium was deposited here by the
steam condensate (conditioning system).
The carbon steel pressure shell was repaired and
after installing a new liner segment the Urea
Reactor was put into service again. However the
structural integrity of the Urea Reactor was not
guaranteed anymore, since there was also risk for
SCC in the bottom part of the Urea Reactor. The
liner compartments in the bottom (not re-lined)
were also cleaned with steam condensate.
83 AMMONIA TECHNICAL MANUAL
 Plant management decided to replace the Urea
Reactor.

Photo 4: Carbon shell after removing liner;

overall corrosion & stress corrosion cracks visible

This example shows that steam condensate must

not be used for cleaning the leak detection
system.

Conclusions
In the high pressure synthesis section of urea
plants the process conditions are very corrosive.

To protect the carbon steel pressure shell from

corrosion, stainless steel liners or weld overlay
are applied. In the case when a liner is applied,
Stamicarbon strongly advises to install a system
for continuous monitoring of leaks in the liner.
Early warning of a leak is essential. Undetected
leaks could lead to catastrophic failure of the
vessel. The leak detection system designed by
Stamicarbon is reliable and able to detect very
small leaks.

Monitoring the leak rate is possible, which

enables plant management to act timely to find
and repair the leak. Reliability of the leak
detection system depends on correct operations
and proper maintenance.

AMMONIA TECHNICAL MANUAL 84 2010